Certain polyol ethers



Oct. 30, 1951 M. DE GROOTE ET AL CERTAIN POLYOL ETHERS Filed Sept. 28,1949 2 SHEETSSHEET 1 GLYCID FIG.2

A C H O 3 6 HYDROPHOBIC REACTANT Melvin De Groofe Arthur F. Wirtel OwenH.Petfingi|l INVENTORS ATTORNEYS 5 O 1951 M. DE GROOTE ET AL 2,572,886

CERTAIN POLYOL ETHERS Filed Sept. 28, 1949 I 2 SHEETS-SHEET 2 lOO/ C H OFIG .3

INVENTORS C3H6O BY ATTORNEYS Patented Oct. 30, 1951 CERTAIN POLYOLETHERS Melvin De Groote, University City, and Arthur F. Wirtel and OwenH. Pettingill, Kirkwood, M0., assignors to Petrolite Corporation, Ltd.,Wilmington, DeL, a corporation of Delaware Application September 28,

The present invention is concerned with certain new chemical products,compounds, or compositions which have useful application in variousarts. It includes methods or procedures for manuf-acturing said newchemical products, compounds or compositions, as well as the products,compounds or compositions themselves.

We have discovered that if one treats alphaterpineol with a combinationof glycid, propylene oxide and ethylene oxide within the proportionshereinafter specified, the mixed alpha-terpineol glycol ether soobtained is an unusually effective demulsifying agent for water-in-oilemulsions, and also has utility in various other arts hereinafterdescribed. One specific example exemplifying the herein contemplatedcompounds is the product obtained by reacting one pound mole ofalpha-terpineol with 7.5 pounds of glycid, and 15 pound moles ofpropylene oxide, followed by reaction with 18 pound moles of ethyleneoxide. Such oxyalkylations are usually conducted in presence of analkaline catalyst, and actually produce a cogeneric mixture. Thisspecific compound, or better still, cogeneric mixture just mentioned, isonly one of a series of similar compounds or mixtures having, in themain, the same general structure or composition.

Previous reference has been made to the fact that the herein specifiedproducts are of particular value for resolving petroleum emulsions ofthe water-in-oil type, that are commonly referred to as cut oil, roilyoil, emulsified oil, etc., and which comprise fine droplets ofnaturally-occurring waters or brines dispersed in a more or lesspermanent state throughout the oil which constitutes the continuousphase of the emulsion.

This specific application or use of our reagents is described andclaimed in our co-pending application, Serial No. 118,411, filedSeptember 28, 1949, now Patent No. 2,549,438,

The compounds or cogeneric mixtures herein described are not only usefulfor breaking oil field emulsions but also are useful for various otherpurposes, such as a break-inducer in the doctor treatment of sourhydrocarbons, as an emulsifying agent, as a component in the preparationof micellar solutions, as an additive to non-hydrocarbon lubricants, asan intermediate for further reaction by virtue of the terminal hydroxylradical, etc.

It is well known that a variety of chemical compounds containing areactive hydrogen atom, i. e., a hydrogen atom attached to oxygen,nitrogen, or sulphur, will react with alkylene oxides,

and sometimes perhaps 1949, Serial No. 118,412

2 particularly ethylene oxide or propylene oxide,

glycid, to yield the corresponding glycol or polyglycol derivative. Suchoxyalkylated derivatives are readily prepared from chemical compounds inwhich the hydrogen atom is directly attached to oxygen, and particularlyin the case of alcohols or phenols such as aliphatic alcohols, phenols,alkylaryl alcohols, alicyclic alcohols, phenoxyalkanols, substitutedphenoxyalkanols, etc. Generally speaking, it has been found advantageousto react a water-insoluble hydroxyl-ated material, having 8 carbon atomsor more, with an alkylene oxide so as to introduce water solubility, orat least, significant or distinct hydrophile character, with the resultthat the derivative so obtained has surface-active properties.

Examples of suitable reactants of this type include octyl alcohol, decylalcohol, dodecyl alcohol, tetradecyl alcohol, octadecyl alcohol,butylphenol, propylphenol, propylcresol, hexylphenol, octylphenol,nonylphenol, and cardanol, as well as the corresponding alicyclicalcohols obtained by the hydrogenation of the aforementioned phenols. Ithas been suggested that at least some of such materials be used in theresolution of petroleum emulsions. As far as we are aware, none of suchmaterials represent products which are acceptable in demulsificationtoday from a competitive standpoint. In the majority of cases suchproducts are apt to be one-sixth, one-fifth, one-fourth, or one-third asgood as available demulsifying agents on the samepercentage-0f-active-material basis, or same cost basis.

We have discovered a very few exceptions to the above general situation.For example, we have discovered if one treats alpha-terpineol withglycid, ethylene oxide and propylene oxide so as to yield a cogenericmixture of glycol ethers, that such mixed derivative has unusualproperties, provided that the composition lies within a certain range,as hereinafter specified. A specific exemplification of this range isthe product obtained by treating one mole of alpha-terpineol with onemole of glycid, then with 15 moles of propylene oxide, and then with 18moles of ethylene oxide. Similarly, one may treat the alphaterpineolwith the 18 moles of ethylene oxide first, and then with the 15 moles ofpropylene oxide next, and finally with glycid.

In subsequent paragraphs from time to time reference is made tocompounds or cogeneric mixtures. At first glance it may appear that suchlanguage is indefinite and, perhaps, contradictory. It is the intentionat the moment only 3 to point out that there is no inconsistency in suchdescription, and that, subsequently, there will be a completeexplanation of why such designation is entirely proper.

As has been pointed out previously the present invention is concernedwith certain reaction products or cogeneric mixtures obtained from fourreactants or components combined in spe cific proportions as hereinafterdescribed in detail. There is no difliculty in setting forth in graphicform a somewhat similar mixture obtained from three components insteadof four, 1. e., from terpineol, for example, either alpha or beta, andethylene oxide and propylene oxide as distinguished from a quaternarymixture employing the same three reactants and-also glycide in addition.

Our co-pending applications, Serial Nos. 109,791, through 109,797,inclusive, all filed August 11, 1949, Serial Nos. 109; 791, 109,794, and109,796, now PatentNos. 2,549,434, 2,549,435,and 2,549,436, and SerialNo. 110,332, filed August 15, 1949, now .Patent No. 2,549,437, describetertiary mixtures lusing the conventional triangular graph. Thetransition from a triangular graph to what would normally be a spacemodel (a regular tetrahedron) followed bysubsequent modification so as.to transform a three-dimensional model within certain limitations to atwo-dimensional plane, presents a certain amount of detailed text andfor this reason what is said subsequently will appear in certain partsor divisions, as follows:

Part 1 is concerned with the importance of ,glycide in affecting thestructure of the derivati-ves, and the method of presentation hereinemployed Withreference to Figures 1, 2, 3 .and4.

Part 2 is in essence the verbatim text as it appears in our co-pendingapplications, Serial Nos. 109,791, 109,792,and 109,793,.a11 filed August11, 1949, and Serial No. 110,332, filed August 15, .1949, and discussesthe preparation of a tertiary mixture from a terpineol, ethylene oxide,and propylene oxide, and discusses its presentation in the form of atriangular graph, together with detailed information as to the chemistryand structures involved.

Part 3 is concerned with the preparation of the compounds employing fourcomponents or four reactants and in imsimplest form perhaps obtainableby treating the tertiary mixtures of Part2 preceding with glycide withinthe range hereinafter specified, i. e., that the final reaction product,or cogeneric mixtures, contain at least 2% and not more'than 2 ofglycide.

Part 4 consists of tables in which thelimiting values are set forth indetail'in tabular form so thatthe invention is set forth withparticularity by this particular means Without necessary referenceto thefigures. Obviously, of course, such tables could not suitably beincorporated in the claims, and such tables represent the outside orlimiting values only and do not include the intermediate values. This isthe reason that the claims refer to the figures.

PART 1 derived from 2 components or 3 components, there is no difiicultyas far as using the plane surface of an ordinary printed sheet. For eX-ample, a 3-component system is usually represented by a triangle inwhich the apexes represent of each component and any mixture or reactionproduct in terms of the 3 components is represented by a point in thetriangular area in which the composition is indicated by perpendicularsfrom such point to the sides. Such representation is employed, forexample, in copending-applications of Melvin DeGroote, Arthur F. Wirteland Owen H. Pettingill, Serial Nos. 109,791, 109,792, 109,793, 109,794,109,795, 109,796 and 109,797, alljfiled August 11, 1949, and Serial No.110,332, .filed .August 15, 1949.

Chemists and physicists ordinarily characterize a ll-component system byusing a solid, i. e., a regular tetrahedron. In this particularpresentation each point or apex represents 100% of each of the 4components, each of the-6 edges represents a line orbinary mixture ofthe 2-components represented by the apexes or points at the end of theline or edge. Each .of the 4 triangles or faces represent a tertiarymixture of the 3 components represented by the '3 corners or apexes andobviously signify the complete absence of the 4th component indicated bythe corner or apex opposite the triangular face.

However, as soon as one movesto-a point .within the regular tetrahedronone has definitely characterized and specified a 4-,component-mixture inwhich the .4 components add up to 100%.

Inaccompanying Figure 1 an attempt is made to illustrate this system ofrepresentation visibly in a plane surface. For sake of convenience oneneed only consider a regular tetrahedron resting on one face ortriangular surface. If somewhere towards the middle of such tetrahedronone places a plane parallel to the base of the tetrahedron one againobtains an equilateral triangle which, of course, is reduced in sizecompared with the equilateral triangle which is the bottomof theregular-tetrahedron. In Figure 1 the tetrahedron may be considered asformed by some transparent material and for convenience the newtetrahedron formed by the passage of the horizontal plane is, of course,a:regu lar tetrahedron also. For convenience, one can consider that heis lookingdirectly at this-tetrahedron which .-is shown somewhatdistorted .for purposeof convenience, and in the smaller regulartetrahedron the apexes are T, U, V and ,}D. The lines are TU, VU, TV andVD. .The four equilateral triangles are I-VD, *UW), TUB and TUD.Bearing'insmind'that this tetrahedron is just the upper part of what isassumedasbeing part of alargertetrahedron and not's'howing, it isassumed :for purpose -of illustration that a point has been selectedwithin this larger tetrahedron to indicate. a specific-mixture composedof 4 components. For convenience, the point is taken as A. If from. Aperpendiculars are erected to each of the four planes then 'there aredesignated at least three of them by lines which are shown :andindicated as follows: A'Bf, A'C', AD. "The fourth perpendicular goesfrom A 'to the point in the plane beneath which is :the assumed base ofthe original larger regular tetrahedron. .Since the larger tetrahedronis not shown for the reason that it would only add confusion, thisperpendicular is indicated simply'by the iline A'-A':A'.

What 'has :been said previously I is illustrated in a's'lightly.differenta'spect actually showing both the large tetrahedron-and theplane in Figure 2. In this instance again the regular tetrahedron mustbe presented in a somewhat distorted aspect in order to show what isdesired. The present invention is concerned with a cogeneric mixturederived from 4 components, to wit, ethylene oxide, propylene oxide,glycide, and hydrophobic reactant which is susceptible to reaction withthe 3 enumerated alkylene oxides. These 4 components or initialreactants represent the 4 points or apexes of the regular tetrahedronand it will be noted that in this presentation the 4 apexes are markedA, B, C and D. A represents 100% of propylene oxide, B represents 100%of ethylene oxide, D represents 100% of glycide and C represents 100% ofhydrophobic reactont.

Referring momentarily to what has been said in regard to Figure 1 itwill be noted that a perpendicular which is comparable is shown as aline connecting point A with point A'A. More important, however, is thisfact, that when a plane is placed parallel to the base such plane ofnecessity has the same configuration as the base. If one selected someparticular figure in the base, for instance, a triangle, square, arectangle, a pentagon, or the like, and drew lines from the corners orapexes of such plane figure in the base, to the top apex D, then thatsame figure but in a reduced size would appear in the intersecting planeTUV shown in this particular figure. TUV is the equilateral trianglefurnished by the intersecting plane WXYZ which interests the regulartetrahedron parallel to the base.

It is convenient to ignore temporarily Figure 3 and pass to Figure 4.Figure 4 again depicts the regular tetrahedron but actually is somewhatdistorted, of course. It also shows a space or block within thetetrahedron and since the block is assumed to be somewhat above thebase, each and every point in this block represents a 4-componentsystem. The present invention is concerned with those compositions whichare characterized and specified by this particular block. As statedpreviously if 3-dimensional models could be employed all that would benecessary would be to prepare the tetrahedron from sheets of plastic sothat 100 sheets, for example, would represent the distance between thebase and the apex, cut out the space represented by the block, and fillit in with colored wax or another plastic, and thus the representationwould be complete. This is not possible due to limitations which havebeen pointed out pretruncated pyramid, that is, E, F, G, and H, does notrest on the bottom of the equilateral base triangle. As has been pointedout previously, point D represents 100% glycide. The base trianglerepresents the three other components and obviously 0% glycide. Forpurpose of what is said herein, the lower base of the truncated pyramid,E, F, G, H, is a base parallel to the equilateral triangle but two unitsup, i. e., representing 2% of glycide. Similarly, the upper base of thetruncated pyramid, I, J, K, L lies in a plane which is 25 units up fromthe base, to wit, represents 25% glycide. Specifically, then, thisinvention is concerned with the use of components in which the glycidecomponent varies from 2% to 25% glycide. The problem then presented isthe determination of the other three components, to wit, ethylene oxide,propylene oxide, and the hydrophobic reactant.

A simplification of the problem of characterizing a 4-component systemwhich enters into the spirit of the present invention is this: If theamount of one component is determined or if a range is set, for example,2% to 25% of glycide,

then the difference between this amount and 100%, i. e., 75% to 98%,represents the amounts of percentages of the other three componentscombined, and these three components recalculated to 100% bases can bedetermined by use of an ordinary triangular graph, such as employed inour previously mentioned eight copending applications, Serial Nos.109,791 to 109,797, inclusive, and Serial No. 110,332.

This becomes even simpler by reference to Figure 1 in which it will beassumed that the amount of glycide is within the range of 2% to 25%, andsince the base of the tetrahedron is an equilateral triangle the planeparallel to the base and through any point on the perpendicular whichrepresents 2% to 25%, must also be an equilateral triangle.

In Figure 1 from the point A there are the three conventionalperpendiculars to the sides as employed in a 4-component system, i. e.,A'B', AC", AB; however, by definition the lines A'B', A'C, and A'D' mustbe perpendicular to the faces. This means that the angles G'D'A', A'CF",and ABE, are right angles. Similarly, the angles DGA, AEB, and AFC'represent the angles between the faces of a regular tetrahedron and thusare constant. Since two angles of the triangle are the same, the thirdangle must be the same and it means that these three triangles aresimilar. This means that the ratio between the perpendiculars to thesides,

that is, A'B', A'C, and A'D' bear the same ratio to each other as theperpendiculars to the edges bear to each other to wit, AE, AF, and AG'.Therefore, when the fourth component, for example, glycide, has been setwithin the range 2% to 25%, the remaining three components consisting of75 to 98% recalculated back to 100% bases, can be calculated orrepresented by the same triangular graph as is conventional and asemployed in the abovementioned co-pending applications, Serial Nos.109,791 through 109,797, filed August 11, 1949, and Serial No. 110,332.

Actually, as far as the limiting points in the truncated pyramid areconcerned, which has been previously referred to in Figure 4, it will benoted that in the subsequent text there is a complete table giving thecomposition of these points for each successive range of glycide. Inother words, a perfectly satisfactory repetition is available by meansof these tables from a practical standpoint without necessarilyresorting to the data of Figure 3.

Figure 3 shows a triangle and the three components other than glycide.These three components added together are less than 100%, to wit, 75%,to but for reasons explained are calculated back to This point isclarified subsequently by examination of the tables. It will be notedalso that in Figure 3 there is shown not only a trapezoid indicated bypoints 8, 9, I 0 and II which represent the bases (top, bottom, or forthat matter, intermediate) of the truncated pyramid, but also area inwhich the composition is of particular efiectiveness as a demulsifier.

The circular and triangular areas can be ignored if desired as far asthe general aspect of the present invention goes, but since-we aremaking direct comparison with our aforementioned co pendingapplications, to wit, Serial Nos. 109,791 to 109,797, inclusive, andSerial No. 110,332, we are employing exactly the same identical figurefor ease of comparison.

. Previous reference has been made to our copending applications, SerialNos. 109,791, to 109,797, inclusive, all filed August 11, 1949, andSerial No. 110,332, filed August 15, 1949. As stated, these wereconcerned with products or coegeneric mixtures obtained from threecomponents-an oxyalkylation-susceptible hydrophobic reactant, ethyleneoxide and propylene oxide. The present invention contains the fourthcomponent, glycide. At first glance it may seem rather odd that theintroduction of glycide in even relatively small amounts radicallyaiiects the nature of the resultant products.

Comparing ethylene oxide, propylene oxide, and glycide, it is to benoted that in ethylene oxide the ratio of carbon atoms to oxygen is 2 to1, in propylene oxide 3 tol, and in glycide 1.5 to 1. This carbon-oxygenratio, of course, explains the greater solidifying eflect of glyeide incomparison with either ethylene oxide or propylene oxide but theprincipal diiference is that in using glycide one can obtain a varietyof branched chain or forked structures.

Assume that the hydrophobic oxyalk-ylationsusceptible reactant has oneor more terminal groups which may be indicated thus:

R simply represents a divalent radical. Reaction with ethylene oxide,propylene oxide and glycide may be shown thus:

n-oznlon R-C3HllOH If one employs ethylene oxide first and then glyoide,or propylene oxide first and then glycide, one obtains an increasedhydrophile effect at the terminal groups for the reason there are twohydroxyls present instead of one, which additionally are susceptible tomore complex micellar formation by virtue of association involving twohydroxyls. This is illustrated in the following manner:

/OH Rs'C2H4OC3H5 It becomes obvious that glycide can be employed in anumber of ways, three of which are as follows: (a) immediately andpreceding the introduction of either ethylene oxide or propylene oxide;(22) after ethylene oxide has been introduced and before propylene oxidehas been introduced, or vice versa; after propylene oxide has beenintroduced and before ethylene oxide has been introduced; and finally(c) glycide can be introduced in a terminal position after both ethyleneoxide and propylene oxide have been introduced. Needless to say, glycidecould be introduced in all three of these positions, or in two of thethree. For that matter some ethylene 8. oxide canbei-ntroduced, thenglycide, and more ethylene oxide, or some propylene oxide, thenglycideand more propylene oxide.

Suggestive of such variations are the following formulas:

O(C2H5O)1.(G3H5O)H For sake of simplicity it appears advisable topresent mixtures obtained from three components first (theoxyalkylation-susceptible hydrophobic reactant, ethylene oxide andpropylene oxide) and then carry the three-component system into thefour-component system by after-treatment with glycide within thestipulated proportions. After such description it becomes obvious thatother modifications of the kind previously sug: gested readily presentthemselves and need only minor description. For this reason the subjectmatter immediately following is in substantially verbatim. form as itappears in our co-pending applications, Serial Nos. 109,791, 109,792,and 109,793, all filed August 11, 1949, and Serial No. 110,332 filedAugust 15, 1949.

PART 2 As has been pointed out previously, for Sim-H plicity ofpresentation and. particularly for convenience of comparison withcertain co-pending applications, particularly Serial Nos. 109,791,109,792, and 109,793, all filed August 11, 1949, and Serial No. 110,332,filed August 15; 1949, the text immediately following is concerned withthe de, rivatives obtained without the use of glycide. The eonversion ormodification of the three-com:- ponent system to a four-component systemis precented in Part 4.

Reference is made to the accompanying Figure 3, in which'there ispresented a triangular graph showing the composition of certain glycolethers of alpha-terpineol, or cogeneric mixtures thereof, derivable fromalpha-terpineol and ethylene oxide alone, or alpha-terpineol andpropylene oxide alone, or alpha-terpineol, and both propyle ene oxide,in terms of the initial reactants. We have found that effectivedemulsifying agents 118. approximately within a small and hithertounsuspected area indicated by the trapezoid determined by the points 8,9, l0 and II. More specifically, particularly effective demulsifyingagents appear within a smaller range, as set forth approximately by thearea, indicated by the segment of a circle in which the area of thesegment is limited'to derivatives in which alpha-terpineol contributesat least 4% by weight of the ultimate compound or cogeneric mixture.

The circle itself is identified by the fact that the points I, 3 and 6appear on the circle. The more effective of these better compounds orcogeneric mixtures are those which appear within the triangle whichrepresents part of the circle and part of the segment, to wit, thetriangle identified by the points I, 3 and B. The most effectivecompounds or cogeneric mixtures of all are those which fall within theinner central triangle of the larger outer triangle identified by thepoints I, 3 and 6, to wit, the smaller triangle identified by the points2, 4 and 5. The most outstanding of these effective compounds orcogeneric mixtures is one which appears to fall substantially at thecenter of the smaller triangle, identified by point I. This particularpoint is obtained by treating one mole of alpha-terpineol with 15 molesof propylene oxide, followed by treatment with 18 moles of ethyleneoxide.

In spite of the unique character of the compounds or cogeneric mixturespreviously described, we have made additionally an invention within aninvention. This can be illustrated by reference to the compounds orcogeneric mixtures whose composition is determined by the inner triange, 2, 4, 5. This preferred class of derivatives, or for that matter, allthe herein described products, can be made in three diiferent ways: (a)by adding propylene oxide first and then ethylene oxide; (b) by addingethylene oxide first and then propylene oxide; or (c) by adding the twooxides by random, indifferent, or uncontrolled addition so as to producea polyglycolether in I which the propylene radicals and ethyleneradicals do not appear in continuous succession but are heterogeneouslydistributed.

We have found that if propylene oxide is added first, and then ethy eneoxide is added, the compounds or cogeneric mixtures. so obtained areinvariably and inevitably more effective as demulsifiers, and are alsomore effective for other purposes than the comparable glycol ethers ofalphaterpineol made by combining the three reactants in any othersequence. This will be explained further with additional illustrationssubsequently.

As an il ustration of the preparation of variouscompounds or cogenericmixtures, and particularly the most desirable ones, and also those whichare helpful in setting the limits in the graph previously referred to,the following examples are included. In connection with these examplesit will be noted that the oxyalkylation of alpha-terpineol, i. e., bytreatment with ethylene oxide or propylene oxide of a mixture of thetwo, is conventional. The procedure is conducted in the same manneremployed in connection with other alcohols or the like, and generally analkaline catayst is employed. See, for examp e, U. S. Patent No.2,440,093, dated April 20, 1948, to Israel, and British Patent No.602,591, applied for February 12, 1945.

Example 1a The reaction vessel employed was a stainless steel autoclavewith the usual devices for heating, heat control, stirrer, inlet,outlet, etc, which is conventional in this type of apparatus. Thecapacity was approximately 40 gallons. The stirrer operated at a speedof approximately 250 R. P. M. There were charged into the autoclave 15.4pounds of alpha-terpineol. There were then added 12 /2 ounces(approximately by weight) of ground caustic soda. The autoclave wassealed, swept with nitrogen gas, and stirring started immediately andheat applied, and the temperature allowed to rise to approximately C. Atthis point addition of propylene oxide was started. It was addedcontinuously at such speed that it was absorbed by the reaction asrapidly as added. The amount of propylene oxide added was 88 pounds. Thetime required to add this propylene oxide was slightly in excess of onehour, about 1% hours. During this time the temperature was maintained at150 to C., using 'cooling water through the inner coils when necessaryand otherwise applying heat if required. At the end of the addition ofthe propylene oxide there was added ethylene oxide, as previouslyindicated. The amount of ethylene oxide added was 80 pounds. operatingconditions, were the same as with the addition of propylene oxide. It isto be noted, however, that ethylene oxide appears to be more reactiveand the reaction seems to require a greater amount of coolin water tohold the temperature range indicated. The time required to add theethylene oxide was about the same, or slightly less, usually just alittle more than an hour.

During the addition of the propylene plus ethylene oxides, the pressurewas held at approximately 50 pounds per square inch gauge pressure, orless. When all the oxide had been added (ethylene oxide being the finaladdition in this particular instance) the autoclave was permitted tostay at the same temperature range for another half hour, even longer ifrequired, or until the gauge pressure had been reduced to zero orsubstantially zero, indicating the reaction was complete. The finalproduct was an oily material, somewhat viscous in nature, resemblingcastor oil and having a definite alpha-terpineol or terpene-like odor.It was soluble in water and also soluble in non-aqueous solvents, suchas aromatic hydrocarbons, and others, although not soluble in somenon-polar hydrocarbon solvents. The final yield was substantially thetotal weight of the initial reactants.

Example 2a The same procedure was followed as in Example la, preceding,except that the order of addition of the oxides was reversed, theethylene oxide being added first and the propylene oxide last. The timeperiod, temperature range, pressure, etc., were kept the same as inExample la, preceding.

Example 3a The same procedure was followed as in Example la, except thata mixture, to wit, 168

pounds of propylene oxide and ethylene oxide,

were added over a two-hour period. This mixture of ethylene oxide andpropylene oxide was obtained from 88 pounds of propylene oxide and 80pounds of ethylene oxide. In this instance again the time range,temperature, and pressure were kept substantially the same as in Example1a, preceding.

Example 4a The same procedure as in Example 1a, preceding, was conductedon a laboratory scale employing a small autoclave having a capacity ofapproximately one liter or up to a 5-gallon size. The amount ofalpha-terpineol employed was 46.2 grams, the amount of propylene oxideemployed was 259.8 grams, and the amount of ethyl- The temperatureemployed, and

11 ene oxide employed was 240 grams. The amount of caustic soda used asacatalyst was 2.33 grams. The operating conditions were substantiallythe same as on alarger scale. Actually the reaction 12 powdered sodium.methylate, equivalent to .5% by weight of the alpha-terpineol which wasemployed.

For reasons which are pointed out hereinafter seemed .to .go faster inthe small autoclave and in greater detail, it is substantiallyimpossible to the time of absorption .couldbe reduced, if de useconventional methods and obtain a single i In m ny instancesabserp Wouldlie-k9 glycol ether of the kind described. Actually, one place in thelaboratory autoclave in a fraction obtains a cogeneric mixture ofclosely related or of the time required in the larger autoclave; intouching homologues. These materials invarifact, many instances,absorption was com ably have high molecular weights and cannot .be pletein 5 to 1D or v minutes, as .compared to separated from one another byany known one-hour on a larger scale. Needless to say, on method withoutdecomposition. The properties a large scale, addition .must'be conducted.careof such a mixture represent the contribution of fully because thereis an obvious hazard in hanthe various individual members of themixture. dling a large quantity of material inan auto- 15 Although onecannot draw a single formula clave which is not necessarilypresent inthe use and say that by following such and such procedof asmall vessel.ure one can obtain 80% or 90% ,or 100% of,su.ch single compound, yet onecan readily draw the 7 Example formulas of a large number of compoundswhich The same procedure was followed as in appear in some of themixtures described elseample 4a, precedingim every respect, exceptwhere, or can be prepared readily as components the Variation describedin Example 2a, preceding, of m1xtures wh1ch are manufactured conveni.e., the ethylene oxide, was added first and the tloniiiuyrepresentme1gmficant ro l .oxide added last portions of various mixtures, are ofdistinct value p FY insofar that they themselves characterize the in-Example .600 vention, i. e., describe individual components The eemeeeeeeeeee wee eeeewee ee 1e Il -3. .23.2ii tfiiififitffitffifiii fiiitii ample 4a in everyinstance, except the modifica- I can representalpha-terpineol, R9 is the ether 3: ggggfi i ggg g Zigz g; 5321 3 g g g3?; radical obtained from alpha-terpineol by removal mixed together andadded in approximately 15 gi g hydrogen atom attached to the Oxygenminutes to one-half hour. In all other respects the procedure wasidentical with that described (1) RO(C2H4O)17(C3H6O) 15H in'Example 4a.M (2) RO(C2H40)18(C3H60)15H The following table includes a series ofcom- (3) RO(C2I-I4O)19(C3H6'O)15H pounds or cogeneric mixtures whichhave been (4) RO(C2H4O)19(C3H6O)15H selected as exemplifying the hereinincluded (5) RO(C2H4O)19(C3H6O) 16H products. Types of the herein notedcompounds (6) RO'(C2H4O)20(C3H6O)16I-I or :cogeneric mixtures have beenproduced in ('7) RO(C2H4O)20(C3H5O)17H three different ways: (a) firstadding the propyl- (8) RO(C2I-I4O)z1(CsH6O)17H ene oxide and then theethylene oxide; (1)) first (9) RO(C3H6O) 15(C2H4O) 17H adding theethyleneoxide and then the propylene (10) RO(C3H6O)15(C2H4O)13H oxide;and (c) mixing the ethylene oxide and the (11) RO(C3H60) 15(C2I-I4O) 19Hpropylene oxide'together andadding them simul- (12) RO(C3H6O) 16(C2H4O)13H taneously. (13) RO(C3H6O)16'(C2H4O) 19H The data are summarized inthe following (14) RO'(C3H60)16(C2H40)20H table: (15)RO(C3HBO)17(C2H40)2OH Alpha-'Terpineol Propylene Oxide Ethylene OxidePoint on w ht Weight Weight m E .N Wt. Wt. Wt. 9353 5515525 use: $5555 2515 5 Grams 3 2 Grams Grams Ether 154 1.0 15.0 462 7.96 45 411 9.34 40 1154 1.0 10.0 771 13.3 50 615 14. 0 40 2 154 1.0 5.0 1700 29.3 55 123228.0 40 5 154 1.0v 10.0 693 11. 95 693 15.77 45 4 154 1.0 5.0 1542 26.61390 31.6 45 5 154 1.0 5.0 1390 23.95 45 1542 35.10 50 6 154 1.0 8.45866 14.95 47. 600 15.17. 44 7 154 1.0 9.2 612 14.0 48.6 704 16.0 42.2154 1.0- 9.0 612 14.0 47.4 746 17.0 43.6 154 1.0 as 812 14.0 46.2 79218.0 45.0 154 1.0 5.7 570 15.0 49.0 748 17.0 43.3 154 1.0 6.45 666 14.9647.55 500 18.17 44 7 154 1.0 8.3 870 15.0 46.7 836 19.0 45.0 154 1.0 8.2934 16.0 49.5 792 18.0 42.3 154 1. 0 8.0 934 16.0 48.5 836 19.0 43.5 1541.0 7.5 934 16.0 47.4 880 20.0 44.8 154 1.0 20.0 200 3. 45 26 416 9.4554 s 154 1.0 4.0 1000 17.25 26 2690 61.2 70 9 154 1.0. 4.0 2925 50.4 76770 17.5 20 10 154 1.0 20.0 462 7.96 154 5.5 20 11 1 Within innertriangular-area. .Duplicated for convenience. Indicates limits oftrapezoidal area. In the preparation of the above compounds the (16)R0(C3H6Ol6(C2H4O)16'(C3H6O)9H alkaline catalyst used was either flakecaustic (17) RO(C3H6O)7(CzH4O')1a(C3H6O) 6I-I sode finely ground withmortar and pestle, or (18) RO(C3H6O 3(C2H4O)15(C3H6O)7H If one selectsany hydroxylated compound and subjects such compound to oxyalkylation,such as oxyethylation, or oxypropylation, it becomes ob vious that oneis really producing a polymer of the alkylene oxide except for theterminal group. This is partlcularly'true where the amount of oxideadded is comparatively large, for instance, 10, 20, 30, 40, or 50 units.If such a compound is subjected to oxyethylation so as to introduce 30units of ethylene oxide, it is well known that one does not obtain asingle constituent, which, for the sake of convenience, may be indicatedas RO(C2H4O) 30H. Instead, one obtains a cogeneric mixture of closelyrelated homologues, in which the formula may be shown as the following:RO(C2I-I4O) 11H, wherein n, as far as the statistical average goes, is30, but the individual members present in significant amount may Varyfrom instances where n has a value of 25, and .perhaps less, to a pointwhere n may represent 35 or more. Such mixture is, as stated, acogeneric, closely related series of touching homologous compounds.Considerable investigation has been made in regard to the distributioncurves for linear polymers. Attention is directed to the articleentitled Fundamental Principles of Condensation Polymerization, by PaulJ. Flory, which appeared in Chemical Reviews, volume 39, No. '1, page137.

Unfortunately, as has been pointed out by Flory and other investigators,there is no satisfactory method, based on either experimental ormathematical examination, of indicating the exact proportion of thevarious members of touching homologous series which appear in cogenericcondensation products of the kind described. This means that from thepractical standpoint, i. e., the ability to describe how to make theproduct under consideration and how to repeat such production time aftertime without difficulty, it is necessary to resort to some other methodof description.

Actually, from a practical standpoint, it is much more satisfactory,perhaps, to describe the ultimate composition in terms of the reactants,i. e., alpha-terpineol and the two alkylene oxides. The reason for thisstatement is the following: If one selects a specific compound, it mustbe borne in mind that such compound is specific only insofar that thecogeneric mixture in terms of a statistical average will conform to thisformula. This may be illustrated by an example such asRO(C3H6O)15(C2H4O)18H. If one combines the reactants in thepredetermined weight ratio so as to give theoretically this specificcomponent, and assuming only one chemical compound were formed, whathappens is that, although this particular compound may be present in asignificant amount and probably less than 50%, actuall one obtains acogeneric mixture oftouching homologues in which the statistical averagedoes correspond to this formula. For instance, selecting 14 reactants,which, at least theoretically, could give the single compoundRO(C3H60)15(C2H40) 18H, what actually happens is that one obtains a sortof double cogeneric mixture, for the reason that in each batch orcontinuous additionof analkyleneoxide a cogeneric mixture is formed.Since the present products require the addition of at least twodifferent multi-molar proportions of each of two different alkyleneoxides (ethylene oxide and propylene oxide) it becomes obvious that arather complex cogeneric mixture must result.

This can be best illustrated by example. Assume that one is going to usethe indicated ratio, to wit, one pound mole of alpha-terpineol, 15 poundmoles of propylene oxide, and 18 pound moles of ethylene oxide. Theinitial step involves the treatment of one pound mole of alpha-.

terpineol with 15 pound moles of propylene oxide so as to yieldtheoretically RO(C3H60)15H; actually, as pointed out, one does notobtain RO(C3H60)1LH in which n is 15, but really one obtains a cogenericmixture in which there are present significant amounts of homologues inwhich n varies from 10, 11 and 12 on up to 17, 18 and possibly 19 or 20.A statistical average, however, must, of course, correspond to theproportion of the initial reactants, i. e., a compound of the formulaRO(C3H60)15H which is present undoubtedly to a significant extent.

When this cogeneric mixture is then subjected to reaction with 18 molesof ethylene oxide, it becomes obvious that, although one may obtain someRO(C3H60)15(C2H40) 18H, yet this particular product can only be presentto a minor extent for reasons which have been described in connectionwith oxyethylation and which now are magnified to a greater degree byoxypropylation. Stated another way, it is probable that the cogenericmixture represents something like R0(C3H6O)1L(C2H4O) n'H in which, aspreviously pointed out, components present in important percentages arethose in which 12 could vary from anywhere beginning with 10 to 12, onup to 18 or 20. By the same token, components present in importantpercentages are those in which 11. could vary anywhere from 13 or 14 upto the lower 20s, such as 21, 22, 23 or 24. Indeed, homologues of alower or a higher value of n and n will be present in minor amounts, thepercentage of such components decreasing, the further removed they arefrom the average composition.

However, in spite of such variation in regard to the cogeneric mixtures,the ultimate composition, based on the ingredients which enter into itand based on the statistical average of such conage formula rather thanthe structure of a single or predominant compound in the mixture.

A second reason for employing a reaction mixture to describe the productis the fact that the molal proportions need not represent whole numbers.We have just pointed out that if one selects molal proportionscorresponding to then the constituents are added in actual molarproportions based on whole numbers. If, how-' ever, one selects a pointin the inner triangular area, which, when recalculated in terms ofmolar:

proportions, produces a fractional number, there is still no reason whysuch proportion of initial 76 reactant should not be adopted. Forinstance} amzcgssc:

one might select a point in the'triangular graph,, which, whencalculated. in. terms of molecular proportions, represents a formula,such as the following: RO(C3H6O')15.5(C2H4Ol1xI-I. This, of course,would be immaterial, for the reason that if one starts with a pound moleofalpha-terpineoli and adds 15.5 pound moles of propylene oxide, onewill obtain, on the average, a mixture closely comparable to the onepreviouslydescribed', usingf exactly 15 pound moles of. propylene oxideinstead of 15.5. Such mixture corresponds to the compoundRO(C3H6O')15.5H only in the sense of the average statistical value, butnot in the sense that there actually can be a compound corresponding tosuch formula. Further discussion of this factor appears unnecessary, inlight of what has beens'aid previously. 7

Such mixture could, of course, betreated with 18 pound moles of ethyleneoxide. Actually, all that has been said sums up to this, and that isthat the most satisfactory way, as has been said: before, of indicatingactual materials obtained by the usual and conventional oxyalkylationprocess is in terms of the initial reactants, and it is obvious that anyparticular point on the triangular graph, from a practical aspect,invariably and inevitably represents the statistical average of severalor possibly a dozen or more closel related cogeners of almost the samecomposition, but representing a series of touching homologues. Theparticular point selected represents at least the composition, of themixture expressed empi'rically in the terms of a compound represent ingthe statistical average.

Previous reference has been made to the fact that comparatively fewox'ya'lkylated derivatives of simple hydroxylated compounds find utilityin actual demulsification practice. We have pointed out that we havefound a very few ex.- cepti'ons to this rule. The fact that exceptionsexists, as in the instant invention, is still exceedingly difficult toexplain, if one examines the slight contribution that the end group,derived from the hydroxylated material, makes to the entire compound.Referring for the moment to a product of the kind which has beendescribed and identified by the formula it becomes apparent that themolecular Weight is in the neighborhood of 1800 and actually the alphaterpineol contributes less than of the molecular weight. As a matter offact, in other comparable compounds the alpha-terpineol may contributeaslittle as 4% or 5% and yet these particular compounds are effectivedemulsifiers. Under such circumstances, it would seem reasonable toexpect that some other, or almost any other, cyclic fi-carbon atomcompound comparable to alpha-terpineol would yield derivatives equallyeffective. Actually, this is not the case. We know of no theory orexplanation to suggest this highly specific nature or action of thecompound or cogeneric mixture derived from alphaterpineol.

Referring to an examination of the previous list of 32 compounds, it isto be noted that in certain examples, for instance, formulas 9 to 15,inclusive, all the propylene oxide is added first and then the ethyleneoxide is added. Compounds indicated by Examples 1a to 8a aresubstantially the same, as far as composition goes, but are reversed,insofar that the ethylen oxide isadded first and. then the propyleneoxide. Other compounds having substantially the same ultimatecomposition, or atleast, very closely related ulti"-- mate compositions,having a further variation in the distribution of the propylene oxideand eth ylene oxide, are exemplified by Formulae 16 to 32, inclusive.

As has been pointed out previously, for some reason which we do notunderstand andfor' which we have not been able to offer any satisfactorytheory, we have found that the best compounds, or, more properly,cogeneric mixtures, are ob*-- tained when all the propylene oxide isadded first tion employing ethylene oxide alone, propyleneoxide alone,or any variation in the mixture of the two, as illustratedby otherformulas. In fact.

the compound or cogeneric mixture so obtained.

as far as demulsification is concerned, is not unfreq'uently at leastone-third better than. any other derivative obtained in the mannerdescribed. involving any of the other above variations.

The significance of what has been said-previously becomes more emphaticwhen one realizes that, in essence, we have found that one isomer is amore effective demulsifyingagent than another isomer. The word isomer isnot exact- 13/ right, although it is descriptive for the purpose.intended insofar that we are not concerned. with a single compound, butwith a cogeneric mixture. which, in its statistical average, correspondsto. such compound. Stated another way, if we start with one pound moleof alpha-terpineol, 15 pound. moles of propylene oxide and 18 poundmoles of ethylene oxide, we can prepare two different. cogenericmixtures, which, on a statistical average, correspond to the following:

and RO(C3H6O)15(C2H4O)18H. There is nothing we know which would suggestthat the latter be a much more effective demulsifying agent than theformer and also that it be more effective for. other industrialpurposes. The applicants have had Wide experience with a wide variety ofsu-rface-active agents, but they are unaware of any other similarsituation, with. theexception of a few instances which are thesubject-matter of other co-pending applications, or under iii--vestigation. This feature represents the invention with an inventionpreviously referred to, and thus, becomes the specific subject-matterclaimed in our co-pendingv applications Serial Nos;

110,332, filed. August 15, 1949, and 109,793,. filed August 11, 1949.

Reference has: been made to: the fact that the.

product herein specified, andparticularly for use.

as a demulsifier, represents a cogeneric mixture of closely relatedhomologues. This does notmean that one could not use combinations ofsuch cogeneric mixtures. For instance, in the previous table data havebeen given for preparation of. cogeneric mixtures which statisticallycorrespond, respectively, to points I, 3 and 6. Such three cogenericmixtures could be combined in. equal weights so as to give-a combinationin which: the mixed statistical average would correspond closely topoint 1.

Similarly, one could do the same thing by preparing cogeneric mixturescorresponding. to-

points 2, 4 and 5, described in the previous table. Such mixture couldthen be combined in equal parts by weight to give another combinationwhich would closely correspond on a mixed statistical basis to point 1.Nothing said herein is intended to preclude such combinations of this orsimilar type.

Throughout this specification reference has been made toalpha-terpineol. We have employed a commercial product sold by theHercules Powder Company under the designation Terpineol 318 whichconsists of 85% alpha-terpineol and beta-terpineol. This mixture meltssufficiently low for the product to be a liquid at ordinarytemperatures, whereas, alpha-terpineol is a mushy crystalline product,which is somewhat more difficult to handle. Terpineol 318 is alsoapproximately one cent a pound cheaper than alphaterpineol. It isunderstood that wherever we have specified alpha-terpineol, thisparticular product can be employed. This, of course, is obvious, for thereason that, if desired, one can mix alpha-terpineol with some otherproduct susceptible to oxyethylation and oxypropylation, such asmenthylcyclohexanol, and subject to two products to simultaneousoxyalkylation. For a number of reasons, it is ordinarily desirable touse a procedure in which only one product is reacted at a time.

At times we have examined samples of Terpineol 318 which appearedacidic, due to the presence apparently of a resinic acid. Attempt tooxyalkylate causes difficulty because the alkaline catalyst isneutralized. In such cases the acidity should be neutralized and thenthe customary amount of catalyst added.

It is possible that the'oxyalkylation, particularly oxypropylation, ofTerpineol 318 is a bit slower than that of straight alpha-terpineol, dueto the presence of beta-'terpineol.

PART 3 As has been pointed out previouslypone way of preparing compoundsor cogeneric "mixtures to be used in the present invention is to preparea series of compounds identified as Examples A through S, in Part 2,preceding, or Examples 1a through 6a, as described in Part 2, preceding.

Referring now to Figure 4, it is obvious that the three components(ignoring glycide) are represented by either the lower trapezoidal basein Figure 4, i. e., E, F, G, H, or I, 'J, K, L and then recalculated to100% basis as a tertiary mixture; such three components must'lie withinthe trapezoid 8, 9, 10, H in Figure 3, and the preferred proportions arewithin the arc'of the circle previously described in Part 2 and'shown inFigure 3, or more specifically within the large triangle 1, 3, 6 or thesmaller triangle, 2, 4, 5, or even more specifically at approximatelypoint I. Stated another way, if one selects the propor'' tion of thethree components or reactants (ignoring glycide) and at any stageemploys sufficient glycide so that on the basis of the quaternarymixture such glycide represents 2% to of the total by weight, then andin that event one has automatically obtained a composition that iswithin the limits of the truncated trapezoidal pyramid identified by E,F, G, H--'I, J, K, L in Figure 4. This represents the cogeneric mixtureor reaction product in terms of initial r'e-, actants with the provisothat the glycide content is 2% to 25% by weight and that 'theremainingthree components recalculated to 100% .basis' (leaving out glycide forthe moment) come within 18 the trapezoidal area indicatedlby 8, 9, III,II on the triangular graph, to wit, Figure 3..

We have prepared derivatives of the kind herein described in a scale.varying from a few ,hundred grams or less, in the laboratory tohundreds of pounds on a plant scale. In preparing. a large number ofexamples we have found it particularly advantageous to use laboratoryequipment .which permits continuous .oxy'propylation. andvoxyethylation. -More specific reference will be made to treatmentwithglycide, subsequently, inthe text. Theoxyethylatipn step is, ofcourse, the same as the oxypropylationstep insofar that two low boilingvliquids are handled in each instance, What immediately follows referst0..oxypropylation and it is understood, that oxyethylationcan behandled conveniently in exactly the same way. The oxypropylatiqn,procedure employed in the preparation of derivatives from,polyhydric re:ac hasbeen ii ly hel me. pa t cularly in light of the. factthatficontinuousoperating p e ure w s employ d. In th s par icula procedurethe autoclave was, a conventionalautoa ade ,0f....st inle s s el, n ha ia acityof app oxima elyon al n. and aworls: s p re. of .LpfiQpol ndsauge p ssure-. Th aut cla was e ipped. withth cqnvsniian evice an vpenings. as, t e, v ab e, sti re p ra ..snee s.. fr9m.. 59 ,B-

9,590 -,.th rm n ter,W land.the m cei eier hanic .tnermo jr; emp yin utlt; pr i sur ..sause...ma u l...rent ine'i.. .=ha fi 1. .1 er nitial acnt atlsa t pnecq necti rld nri n 9m i ,a tr ene. Ox de} i p e eo ide tothe .bqttem i. the aut c e ong w th, r uitabla eri ss for th l ls n hean ih 1 t 91aila.$uh. as a eeeli l a ke n pref a lyls ls a 1 here wi thJacke sq rran e t atlt s mt ee s h st a 09 1 5 wi was. arid m theirequipped with electrical heating crevices. Such autoclaves are, ofcourse, essence sham scale replicas of the usual conventional autoclavese l jnerralk latie ,p e i C ntinuou erates eb tim 5. o sr t en is eqbiees i y h 'i a tarate containerto hold the all yleiie' oxide beingmploredr a ii iilar rqfiy bi d T 29?! tamer i s es ent l y-9 e.. t6having a capacity-of aboutone-half gaubm or ewha j n excess ,.fih ?'i eTh s 1 was equipped, also, with an inlet for charging, andan outlet tubegoing to the bottom' ofth'e" container so as to permit o f alk'yleneoxide in h qui ha etq th i oela Q e itional equipmentconsists, ofcourse, of the nip re di c. res reseuser ish e d glass) e?"- momonnection f r ,n q s r pressuring bomb, etc. The bomb wasplaced on ascale dur; 5 dthepere ti b w n t e bplfib n th au ar w r flex ble .sta ei r tubing. so 4 that continuous Weighings could be made withoutbreaking or making any connections. This also applied to the nitrogenline, wh h w s. used t r ssur th bom e r rhe. e nt th t it req d ni t eal c n en on l P oc dur 9r 'd tiea ic provided greater safety was used,of course, such as safety s e r mt et r e s re e,

. W this tic lararra seme t ct l y all oxypropylations becameuniform in.that -the reaction temperature could be held within a few degrees ofany points'elected' in this particular rangerforinstance, in most caseswe have selected a point of approximately 160 C. to 165 0., as beingparticularly desirable and stayed within the range of 155 to 180 C.almost invariably. The propylene oxide was forced in by means ofnitrogen pressure as rapidly as it was absorbed, as indicated by thepressure gauge in the autoclave. In case the reaction slowed up so thetemperature dropped much below the selected point of reaction, forinstance,160 0., then all that was required was that either coolingwater was cut down or steam was employed, or the addition of propyleneoxide speeded up, or electric heat used in addition to the steam inorder that the reaction procedures at or near the selected temperaturesbe maintained.

Inversely, if the reaction proceeded too fast the amount of reactantbeing added, i. e., propylene oxide, was cut down or electrical heat wascut off, or steam was reduced, or if need be, cooling water was runthrough both the jacket and the cooling coil. All these operations, ofcourse, are dependent on the required number of conventional gauges,check valves, etc., and the entire equipment,'as has been pointed out,is conventional and, as far as I am aware, can be furnished by at leasttwo firms who specialize in the manufacture of this kind of equipment.

Attention is directed to the fact that the use of glycide requiresextreme caution. This is particularly true on any scale other than smalllaboratory or semi-pilot plant operations. Purely from the standpoint ofsafety in the handling of glycide, attention is directed to thefollowing: (a) If prepared from glycerol monochlorohydrin, this productshould be comparatively pure; (b) the glycide itself should be as pureas possible as the efiect of impurities are difficult to evaluate; (c)the glycide should be introduced carefully and precaution should betaken that it reacts as promptly as introduced, 1. e., that no excess ofglycide is allowed to accummulate; (d) all necessary precaution shouldbe taken that glycide cannot polymerize per se; (6) due to the highboiling point of glycide one can readily employ a typical separatableglass resin pot as described in the co-pending application of MelvinDeGroote and Bernhard Keiser, Serial No. 82,704, filed March 21, 1949,now Patent 2,499,370, granted March 7, 1950, and offered for sale bynumerous laboratory supply houses. If such arrangement is used toprepare laboratory scale duplications, then care should be taken thatthe heating mantle can be removed rapidly so as to allow for cooling; orbetter still, through an added opening at the top the glass resin pot orcomparable vessel should be equipped with a stainless steel cooling coilso that the pot can be cooled more rapidly than mere removal of mantle.If a stainless steel coil is introduced it means that conventionalstirrer of the paddle type is changed into the centrifugal type whichcauses the fluid or reactants to mix due to swirling action in thecenter of the pot. Still better, is the use of a laboratory autoclave ofthe kind previously described in this part; but in any event, when theinitial amount of glycide is added to a suitable reactant, suchassorbitol, the speed of reaction should be controlled by the usualfactors, such as (a) the addition of glycide; (b) the elimination ofexternal heat, and use of cooling coil so there is no undue rise intemperature. All the foregoing is merly conventional but is included dueto the hazard in handling glycide.

Example 1b It is to be noted that the procedure followed can beconducted on any convenient scale, that is, on either a small laboratoryscale, semi-plant plant scale, pilot plant scale, or large plant scale.We have conducted experiments employing equipment of all such varioussizes. Our preference even on a laboratory scale is to use continuousintroduction of ethylene and propylene oxide, although this is notnecessary. The introduction may be batchwise. Previous reference hasbeen made to the catalyst used in connection with ethylene oxide andpropylene oxide. These same alkaline catalysts, particularly causticsoda, caustic potash, sodium methylate, etc., are usually satisfactorywith glycide which in many ways seem to be at least as reactive asethylene oxide and possibly more reactive than propylene oxide.

The reaction vessel employed was a stainless steel autoclave with theusual devices for heating, heat control, stirrer, inlet, outlet, etc.,which is conventional in this type of apparatus. The capacity wasapproximately 40 gallons. The stirrer operated at a speed ofapproximately 250 R. P. M.

The particularly piece of equipment employed was adapted for the use ofglycide without pressure, as well as the use of ethylene oxide andpropylene oxide with pressure. Stated another way, instead of serving asan autoclave only it was also equipped with a water cooled condenserwhich could be shut ofi when used as an autoclave. It was equipped alsowith an equivalent of a separatory funnel and an equalizing pressuretube so that a liquid such as glycide could be fed continuously at adropwise or faster rate into the vessel and the rate controlled byvisual examination. For convenience, this piece of equipment will bereferred to as an autoclave.

There were charged into the autoclave 15.4 pounds of alpha-terpineol.There were then added 12.5 ounces (approximately 5% by weight) of groundcaustic soda. After being charged the autoclave was sealed, swept withnitrogen gas, and stirring started immediately and heat applied, and thetemperature allowed to rise to approximately C.

The glycide employed was comparatively pure. 7.5 pounds of glycide wereused. This was charged into the upper reservoir vessel which had beenpreviously flushed out with nitrogen and was the equivalent of aseparatory funnel. The glycide was started slowly into the reaction massin a dropwise stream. The reaction started to take place immediately andthe temperature rose approximately 10 to 15. Cooling water wasrunthrough the coils so that the temperature for addition of glycide wascontrolled within the range roughly of 110 to C. The addition wascontinuous within limitations and all the glycide was added in less thantwo hours. This reaction took place at atmospheric pressure with simplya small stream of nitrogen passing into the autoclave at the very topand passing out through the open condenser so as to avoid any possibleentrance of air. When the reaction was complete this condenser was shutoff and also the opening to the glycide inlet and to the equalizingline. The equipment was used as an autoclave during the addition ofpropylene oxide and ethylene oxide. In other words, the equipment wasoperated under pressure. At this point addition of propylene oxide wasstarted. It was added continuously at such speed that it was 7 absorbedby 'the reaction'as rapidly as added.

21 oxide was slightly-in-excess of onehounabou-t 1% hours. During thistime the temperature was maintained at 150 to 160 C., using coolingwater through the inner coils when necessary and otherwise applying heatif required. At the end of the addition of the'propylene oxide there wasadded ethylene oxide, as previously indicated. The amount of ethyleneoxide added was 80 pounds. The temperature employed, and operatingconditions, were the same as'with the addition of propylene oxide. It isto be noted, however, that ethylene oxide appears to be more reactiveand the reaction seems to require a.

greater amount of cooling water to holdthetemperature range indicated.The time required to add the ethylene oxide was about thesame orslightly less, usually just a little. more than an hour.

During the addition of the propylene and ethylene oxides, the pressurewas held at approximately 50 pounds per square inch gauge pressure, orless. When all the oxide had been added (ethylene oxide being the finaladdition in this particular instance) the autoclave was permitted tostay at the same temperature range for another half hour, even longer ifrequired, or until the gauge pressure had been reduced to zero orsubstantially zero, indicating the reaction was complete. The finalproduct was an oily material, somewhat viscous in nature, resemblingcastor oil and having a definite'alphaterpineol or terpene-like odor. Itwas-soluble in water and also soluble in non-aqueous solvents, such asaromatic hydrocarbons, and others, although not soluble in somenon-polar hydrocarbon solvents. The final yield was substantially thetotal weight of the initial reactants.

Example 2b The same procedure was followed as in Example 1b, preceding,except that the order of addition of the oxides Was-reversed, theethylene oxide being added first and the propylene oxide added last. Thetime period, temperatuiaerange, pressure, etc., were kept the same as inExample 11;, preceding.

Example 3b When all the glycide had been added in approxi-- mately a2-hour period of time, the connections were changed so that the ethyleneoxide was added. The amounts employed, operating conditions, etc., werethe same as in Example lb.

I The same procedure was followed as in 'Example. 3b, preceding, exceptthat the stages of addition of ethylene oxide and propylene oxide werereversed, that is, the ethylene oxide was. added as the first stage,using the equipment; as an autoclave, then theg'lycide was. added, and

then the'propylene oxide, The amounts used,

operating conditions, etc., were identically' the same as in Example 15,preceding, except for the order of addition.

Example 5b The co-generic mixture obtained from Example la, in Part 2,preceding, was treated with 7.5 pounds of glycide in the mannerdescribed in Example 15, preceding. It is to-be noted that in essencethis is'simply another variation of Example lb, in which the equipmentis used as an autoclave, first to add the propylene oxide and then toadd the ethylene oxide, and thenthe glycide when-using the equipmentwith a condenser open to the atmosphere with a slow stream of nitrogenpassing through to prevent entrance of air.

Example 6b The product obtained from Example 2a in Part 2, preceding,was treated with 7.5 pounds of glycide in the manner described inExample 11), preceding. It is to be noted that this example again issimply a variation of Example 1b, in which the ethylene oxide was addedfirst and then the propylene oxide. During these two additions theequipment was used as an autoclave and then the customary change madeand glycide added to the extent of 7.5 pounds in the manner described inExample 11), preceding.

Example 7b The same procedure was followed as in Example lb with thefollowing change. After the glycide was added the propylene oxide andethylene oxide were added as a mixture (158 pounds). This mixture ofethylene oxide and propylene oxide was obtained from 88pounds ofpropylene oxide and pounds of ethylene oxide. In this instance, again,the time range, temperature, and pressures were kept Substantially thesame as in Example 1b, preceding.

Example 8b The product obtained from Example 3a described in Part 2,preceding, was treated with 7.5 pounds of glycide in the mannerpreviously described under the heading of Example 1b. This is in essencesimply a variation of Example 7b in which the mixed ethylene oxide andpropylene oxide are added,'using the equipment'first as an autoclave,and then the glycide is added subsequently in'the customary manner aspreviously described.

Example 9b The examples previouslydescribed as Examples lb, through 85,inclusive, were repeated making the following change. The amount ofcatalyst added, instead of being 12.5 ounces was increased to 14 ounces.The amount of glycide used, in-. stead of being 7.5 pounds was increasedto 15 pounds. The conditions under which the glycide was added were thesame as inprevious examples but required approximately 3 /2 hoursinstead of 2 hours for the addition of glycide. The amounts of ethyleneoxide and propylene oxide and terpineol were kept constant. 7

Example 10b The same procedure as in Example 1?), preceding,wasconducted on a laboratory scale employing a small autoclave having acapacity of approximately one liter, or up to a 5-gallon size.

23- The amount of alpha-terpineol employed was 46.2 grams, the amount ofglycide employed was 22.5 grams, the amount of propylene oxide employedwas 260 grams, and the amount of ethylene oxide The amount of causticemployed was 240 grams. soda used asacatalyst was 2.4 grams. which theproportion of the reactants cor- The operating conditions weresubstantially the responded to Example A in Part 2 bear the same same ason-a larger scale. Actually the reaction A indication, for instance, AA.Those which seemed to go faster in the small autoclave and correspond toB, bear the same B indication, for the time of absorption could bereduced, if deinstance, BBB. The table immediately precedsired. In manyinstances absorption would take ing shows the order in which thereactants were place in the laboratory autoclave in a fraction of addedto the terpineol. On the left-hand side the time required in the largerautoclave; in fact, are those prepared using one mole of glycide for inmany instances, absorption was complete in 5 each mole of terpineol. Onthe right-hand side to 10 or minutes, as compared to one hour on 15 areincluded experiments where two moles of glya larger scale. Needless tosay, on a large scale, cide were used, and the Figure 2 precedes theletaddition must be conducted carefully because ters AA, BBB, CCCC, etc.As indicated in this there is an obvious hazard in handling a largetable, spot checks were made across the board inquantity of material inan autoclave which is not sofar that it would have been impossible toprenecessarily present in the use of a small vessel. pare all thepossible modifications.

Emmple 11b Incidentally, the physical appearance of the materialsobtained using glycide in addition to The examples conducted on a largescale in ethylene oxide and propylene oxide is substan- Examples 22) to9b, inclusive, were repeated on a tially the same as those obtained inwhich glysmall scale, using the same amount of the in- 25 cide is notused. There is no marked difierence gredients above indicated, except inthe subseinphysical appearance and glycide does, of course, quentexperiments where twice as much glycide add a greater proportion ofwater solubility. was employed, and in such instances the amountNeedless to say, visual examination, or simple 0f yc Was 4 grams ste of22 ams, a physical tests do not reveal the difierences in t e amou t Ofa y u w t t s la ger structure pointed out in Part 1. Thesepolyglyamount of glycide was 2.75 grams. In all other col ethers arecomparatively thin liquids, somerespects all the variants were conductedin the times showing only modest viscosity, and the color same manner aspreviously described except that varies from almost water-White to paleamber. oxyethylation and oxypropylation took place The color seems to bedue to impurities and is a much more rapidly, frequently in a matter oftrace of iron getting into the compound during minutes as indicated, andthe addition of glycide took place in less time, requiring 15 minutes toapproximately minutes.

oxide and glycide. Needless to say, hundreds of variants within thespecification of the invention are possible. Not all could be prepared.A number of those prepared are indicated in the table which appears inPart 2. All the experiments in the process of manufacture, or may bepresent in the catalyst. The products, of course, show a considerablerange of insolubility, from a stage Glycide equal to mol to mol ofterpineol Reactants Other than Glycide as Glycide equal to 2 moles permol of terpineol reported in table in Part Two Glycide (1) Pr() (1) H0(1) PrO (2) Glycide (2) EtO (2) EtO (3) EtO (3) Glycidc (3) See thetable which appears in Part 2, preceding. This same series ofexperiments were repeated, using the same equipmentand procedure asdescribed in Examples 10b and 11b. The amount of ethylene oxide wasequal to the terpineol in a molal ratio or else two moles were employedfor each mole of terpineol. In the preparation of these compounds thealkaline catalyst was either flake caustic soda finelyground with molarand pestle, or powdered sodium methylate equivalent to 6.7% of theterpineol employed. In these experiments the glycide was added at threedifferent points and reacted immediately with terpineol; or theterpineol was reacted with propylene oxide and then with glycide, andthen with ethylene oxide; or the terwhere they are dispersible ormiscible, to products which, at least in dilute solution, have anapparently homogeneous or transparent appearance. The odor, if any, isgenerally suggestive of a terpene or similar product.

PART 4 pineol was reacted with propylene oxide, ethylene 7 tetrahedralpyramid depicted in Figure 4 and de- '25 fined by E, F, G, HI,.J; K, L.However, for convenience, referring .tothe table which includes Athrough S in Part 2, it is to be noted that the initial mixture employs15 parts of terpineol 45 parts of propylene oxide-and 40 parts ofethylene l oxide. In the second example there'are employed parts ofterpineol, 40 parts ethylene oxide, and 50 parts propylene oxide. 'Thetable shows the mixture with the three-component.constituent (whenrecalculated back to 100% basis) and the corresponding figure when 1 to25% glycide is present. The tables are self-explanatory and illustratecompositions which set the boundary or limiting compositions. We havespot checked such compositions and prepared a substantial number but arenot including them for the reason that such inclusion would be onlyrepetitious over and above what' has been said previously.

TAB LE A Table for Ex. A series-point 1 on triangular graph (Figure 3)Per Cent- Remaining g i ggag fig i t P G t 3 g g lated Back to Ali w eren on main; ar rap Per Cent Remaim for Per Cent Glyc d Glycid 8 3Reactanps Alpha Alpha.

'Ier- EtO PrO Ter- E120, PrO pineol pineol 99 15 40 45 14. 8 39. 6 44.98 15 40 45 14. 7 39. 2 44. 97 15 40 45 14. 5 38. 8 43. 96 15 4O 45 14.4 38. 4 43. 95 15 40 45 14. 2 38. 0 42. 94 15 40 45 14. 1 37. 6 42. 9315 40 45 13. 9 37. 2 41. 92 15 .40 45 13.8 36.8 41. 91 15 40 -45 13; 636. 4 41. 90 15 40 45 13. 5 36. 0 40. 89 15 '40 l 45 13. 3 35. 6 40. 8815 "40 45 13. 2 35. 2 39. 87 15 '40 45 13. O 34. 8 39. 86 15 40 45 12. 934. 4 38. 85 15 40 45 12. 7 34.9 38. 84 15 40 45 12. 6 33. 6 37. 83 1540 45 12. 4 33; 2 37. '82 15 40 45 12. 3 32; 8 36. 81 15 40 45 12. 1 32.4 36. 80 15 40 45 12. 0 32. 0 36. 79 15 40 45 11. 8 31'. 6 35. 78 15 4045 11. 7 31; 2 35. 77 15 40 45 11. 5 8 34. 76 15 11. 4 30.4 '34. 75 1540 45 11. 2 39. 4 33.

TABLE B Table for Ex. B series-paint 2 on triangular graph (Figure 3)Per Cent Remaining g igsagfig ggfi 3 Reaetants Based lated Back to AllowPer Cent on Triangular Graph r Pe CentGl id Per Cent Remain- 0 r WGlycid ing 3 Reactants Alpha Alpha I Ter- .EtO PrO Ter- 'EtO PrO pineolpineol 99 '10 40 9. 9 39. 6 49. 5 98 10 40 50 9. 8 3 2 49. 0 97 10 4O 509. 7 '38. 8 48. 5 96 10 40 50 9. 6 38. 4 48. 0 95 10 40 50 9. 5 38. 047. 5 94 10 40 50 9. 4 37. 6 47. 0 93 10 40 50 9. 3 37. 2 46. 5 92 10.40 50 9. 2 36. 8 46. 0 91 10 40 50 9. 1 36. 4 45. 5 9O 10 40 50 9. 036. 0 45. O 89 10 40 50 8. 9 35. 6 44. 5 88 10 40 50 8. 8 35. 2 44. 0'87 10 40 50 8. 7 34. 8 43. 5 86 1O 4O 50 8. 6 34. 4 43. 0 85 10 40 5O8. 5 34. 0 42. 5 84 10 40 50 8. 4 33. 6 42. 0 I 83 10 40 50 8. 3 33. 2..41. 5 I 82 10 40 50 8. 2 32. 8 .41. 0 81 10 r 40 5O 8. 1 32. 4 40. 580 10 40 50 8. 0 32. 0 40. 0 79 10 40 p 50 7. 9 31.6 39. 5 78 10 40 507. 8 31. 2 39. 0 Y 77 10 40 50 7. 7 30. 8 38. 5 76 10 40 "50 7. 6 30.438.0 10 40 5O 7. 5 30. 0 37. 5

TABLE. 0 Table for Ex. O. series poi'ht 8 0a triangular graph (Figure 3)Per Cent Remaining Per Cent Remaining w 12.542.145. 59... Per Cent ggigf on Tnangular Graph for Per Cent Glycid Glyc'id ing 3 ReactantsAlpha 7 Alpha Ter- EtO PrO Ter- EtO PrO pineol pineol 99 5 40 55 4. 939. 6 '54'. 5 98 5 40 55 4.9 39.2 --53.9 97 5 40 55 4. 8 38.8 53. 4 96 540 55 4.8 "38.4 5218 95 5 40 55 4.7 -38.0 52.3 94 5 40 55 4. 7 37.6 51E7 93 5 40 55 4.6 37.2 51.2 92 5 40 55 4.6 36.8 50.6 91 5 40 55 4. 5 36.4 50. 1 90 5 40 55 4.5 36.0 49.5 89 5 40 55 4. 4 35. 6 r 49. 0 88 5 4055 4. 4' 35. 2 48. 4 87 5 40 55 4. 3 34. 8 47 9 86 5 40 55 4.3 34.4 47.385 5 4O 55 4. 2 34. 0 46. 8 84 5 '40 55 4.2 i 33. 6 46. 4 83 5 40 55 4.133.2 45.7 82 5 40 55 4.1 32.8 45.1 81 5 C40 55 4.0 32. 4 44.6 I 5 40 554.0 32. 0 44. 0 79 5 40 55 3. 9 31. 6 43.5 78 5 40 55 3.9 :3112 42.9 775 49 55 3. 8 30. 8 42.4 76 6 40 55 3. 8 30.4 41.8 75 6 j 40 55 3. 7 30.041.3

TABLE D Per Cent Remaining 3 Reactants Based Per Cent Remaining 3Reactants calculated Back to Allow Per Cent 1521' B33315 on TriangularGraph for Per 0 ent-61Wid Glycid h1g3; Reactants Alpha v Alpha 7 .Ter-EtO PrO Ter- EtO PrO pineol pineol 99 1O 45 I :45 9. 9 44.6 44.5 98 1045 45 9.8 44.1 44.1 .97 3 10 45 45 9. 7 43.7 43. 6 96 10 45 45 9. 6 43.243. 2 95 10 45 45 9. 5 42. 8 43. 7 '94 i '10 v 45 45 9.4 4 2.3 42.3 9310 45 45 9. 3 41. 9 41. 8 92 10 45 45 9. 2 41. 4 41. 4 91 10 45 45 9. 141.0 40.9 '90 I 10 45 '45 9. 0 40. 5 40. 5 89 10 45 45 8.9 40.1 40.0 8810 45 45 8.8 39. 6 39.6 87 10 45 45 8. 7 39. 2 39. 1 86 10 45 45 8.638.7 38. 7 10 45 '45 8. 5 38. 3 38.2 84 '10 45 45 8. 4 37. 8 37. 8 83 1045 '45 8.3 37.4 37.3 82 1O 45 45 8. 2 36.9 36.9 81 10 45 45 8.1 36.536.4 '80 I 10 45 45 8.0 36. 0 36.0 "79 10 .45 '45 7. 9 35.6 35.5 78 1045 '45 7. 8 35.1 35. 1 77 10 '45 45 7. 7 34. 7 34.6 76 10 45 45 7.6 34.234.2 75 10 I 45 45 7.5 33.8 33.7

'TABLE E Per Cent Per Cent Remaining 3'Reactants Based Per CentRemaining 3 Reactants Calculated Back to Allow Cent Remaim on TriangularGraph for Per Cent Glycid Glycid 7 ing 3 Reactants Alpha Alpha Ter- EtOPrO Ter- .EtO PrO pineol pineol 99 5 45 5 50 4. 9 .44. 6 49.5 98 5 45 504. 9 44. 1 49. 0 97 5 45 50 4. 8 43. 7 48. 5 .96 5 45 50 4. 8 43. 2 48.05 45 I 50 4. 7 42.8 47. 5 94 5 45 50 4.7 42.3 47.0 93 5 50 4 6 41. 9'46. 5 92 "5 r 45 50 4.6 .41.4 146.0 91 5 :45 I 50 4. 5 41. 0 :45. 5 1.90 5 -45 50 4.5 .40. 5 .45. 0 89 5 .145 50 4.4 40.1 "14.5 88 5 45 50 4.4 39. 6 44. 0 '87 5 "45' "50' 4'. 3 39. 2 '43. 5

TABLE JConti-nued Table for E2. J series-120M510 rm triangular graph(Figure 8) Per Cent Remaining g gggg i g ggg g 3 Reactants Calcu- PerCent on Triangular Graph gg gg gg g g Per Cent Remainye Glycid ing 3Reactants Alpha Alpha 7 Ter- EtO Pr Ter- EtO PrO pineol pineol 88 4 2076 3. 6 17. 6 66. 8 87 4 20 V 76 3. 17.4. 66. l 86- I 4 20' 76 3. 5'17.2 I 65.3 85 4 20, Y 76 3. 4 17. 0 64. 6 84 4 20 76 3. 4. 16. 8 ,63. 883 4 20 76 3. 4 16. 6 i 63. 0 82 4 20 76 3. 3 16. 4' 62. 3 81 4 20, 763. 3 16.2 61. 5 80. 4 20' 76 3.2 16.0 60.8 79 V 4; 20 76 3. 11115.8 60.1 78' 4 20 76 3.2 '15.6 59.2 77 4 20 76 3.0 15. 4 58. 6 76 4 20 76 3. 015. 2 56. 8 75 4 20 76 3. 0 15. 0 57. 0

TABLE K Table for E0. K series-point 11 on Triangular Graph (Figure 3)Per Cent Remaining g igsag fig gz fifi P C t 3 g fi g g lated Back toAllow Per Cent fi i on nang r tap for Per Cent Glycid Glycid ing 3Reactants Axpha Alpha Ter- EtO PrO Ter- EtO PrO pineol pineal 99 20 2060 19. 8 19. 8 59. 4 98 20 20 60 19. 6 19. 6 58. 8 97 20 20 60 19. 4 19.4 58. 2 96 20 20 60 19. 2 19. 2 57. 6 95 20 20 60 19. 0 19.0 57. 0 94 2020 60 18. 8 18. 8 56. 4 93 20 20 6O 18. 6 18. 6 55. 8 92 20 20 60 18. 418. 4 55. 2 91 20 20 60 18. 2 18. 2 54. 6 90 20 20 60 18. 0 18. 0 54. 089 20 20 60 17. 8 17. 8 53. 4 88 20 2O 60 17. 6 17. 6 52. 8 87 20 20 6017. 4 17. 4 52. 2 86 2O 20 60 17. 2 l7. 2 51. 6 85 20 20 60 17. 0 17. 051. 0 84 20 20 60 16. 8 16. 8 50. 4 83 20 20 60 16. 6 16. 6 49. 8 82 2O2O 60 16. 4 16. 4 49. 2 81 20 20 60 16. 2 16. 2 48. 6 8O 2O 20 60 16. 0l6. 0 48. 0 79 2O 20 60 15. 8 15. 8 47. 4 78 20 20 60 15. 6 15. 6 46. 877 20 20 60 15. 4 15. 4 46. 2 76 20 20 60 15. 2 15. 2 45. 6 75 20 20 6015. 0 15. 0 45. 0

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

1. At least one cogeneric mixture of a homologous series of glycolethers of alpha-terpineol; said cogeneric mixture being derivedexclusively from alpha-terpineol, glycide, ethylene oxide and propleneoxide by reaction thereof in such weight proportions so the averagecomposition of said cogeneric mixture stated in terms of initialreactants lies approximately within the truncated trapezoidal pyramididentified as E, F, G, H- I, J, K, L in Figure 4 of the drawings, withthe proviso that the percentage of glycide is within the limits of 2% to25% by weight and that the remaining three initial reactants,recalculated to a 100% basis, lie approximately within the trapezoidalarea defined approximately in Figure 3 of the drawings by points 8, 9,I0 and H.

2. A cogeneric mixture of a homologous series of glycol ethers ofalpha-terpineol; said cogeneric mixture being derived exclusively fromalpha-terpineol, glycide, ethylene oxide and propylene oxide by reactionthereof in such weight 'fproportionsso the average composition-of saidcogeneric mixture stated in terms of initial re- --actants--liesapproximately within the truncated trapezoidal pyramid identified as" E,F, G, H

' I; J K, L in Figure 4 of the drawings, with the provisothat'thepercentage of glycide is within the'limits-of 2% to 25% by weight andthat the remaining three initial reactants, recalculated to ofthe'drawings by points 8,9, l9 and H.

A cogenericmixture of a homologous series -of-. glycol ethers; ofalpha-terpineol; said co- "'g'eneriomixturebeing derived exclusivelyfrom 15;

alpha-terpineol, glycide, ethylene oxide and propylenepxide by reactionthereof in such weight proportions so-the average composition of saidcogeneric mixture stated in terms of initial reactants liesapproximately within the truncated trapezoidal pyramid identified as E,F, G, H I, J, K, L in Figure 4 of the drawings, with the proviso thatthe percentage of glycide is within the limits of 2% to 25% by weightand that the remaining three initial reactants, recalculated to a basis,lie approximately within the segment of the circle of 'the drawing inwhich the minimum alpha-terpineol content is at least 4% and whichcircle is identified by the fact that points I, 3 and 6 lie on itscircumference, as shown in Figure 3 of the drawings.

4. A cogeneric mixture of a homologous series of glycol ethers ofalpha-terpineol; said cogeneric mixture being derived exclusively fromalpha-terpineol, glycide, ethylene oxide and propylene oxide by reactionthereof in such weight proportions so the average composition of saidcogeneric mixture stated in terms of initial reactants liesapproximately within the truncated trapezoidal pyramid identified as E.F, G, H- I, J, K, L in Figure 4 of the drawings, with the proviso thatthe percentage of glycide is within the limits of 2% to 25% by weightand that the remaining three initial reactants, recalculated to a 100%basis, lie approximately within the triangular area defined in theaccompanying drawing by points I, 3 and 6, as shown in Figure 3 of thedrawin s.

5. A cogeneric mixture of a homologous series of glycol ethers ofalpha-terpineol; said cogeneric mixture being derived exclusively fromalpha-terpineol, glycide, ethylene oxide and propylene oxide by reactionthereof in such weight proportions so the average composition of saidcogeneric mixture stated in terms of initial reactants liesapproximately within the truncated trapezoidal pyramid identified as E,F, G, ,HI, J, K, L in Figure 4 of the drawings, with the proviso thatthe percentage of glycide is within the limits of 2% to 25% by weightand that the remaining three initial reactants, recalculated to a 100%basis, lie approximately within the triangular area defined in theaccompanying drawing by points 2, 4 and 5, as shown in Figure 3 of thedrawings.

6. A cogeneric mixture of a homologous series of glycol ethers ofalpha-terpineol; said cogeneric mixture being derived exclusively fromalpha-terpineol, glycide, ethylene oxide and propylene oxide by reactionthereof in such weight proportions so the average composition of saidcogeneric mixture stated in terms of initial reactants liesapproximately within the truncated trapezoidal pyramid identified as E,F, G, HI, J, K, L in Figure 4 of the drawings, with the proviso that thepercentage of glycide is within r the limits of 2% to 25% b weight andthat the Figure 3 of the drawings.

7. A single cogeneric mixture of a homologous series of glycol ethers ofalpha-terpineol; said cogeneric mixture being derived exclusively fromalpha-terpineol, glycide, ethylene oxide and propylene oxide by reactionthereof in such weight proportions so the average composition of saidcogeneric mixture stated in terms of initial reactants liesapproximately within the truncated trapezoidal pyramid identified as E,F, G, I-I-I, J, K, L in Figure 4 of the drawings, with the proviso thatthe percentage of glycide is within the limits of 2% to 25% by weightand that the remaining three initial reactants, recal- 32 culated to a100% basis lie approximately at point 1 in the Figure 3 of the drawings.

MELVIN DEGROOIE. ARTHUR F. WIRTEL. OWEN H. PET'I'INGILL.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,976,677 Wittwer Oct. 9, 19342,130,525 Coleman et a1. Sept. 20, 1938 2,176,834 Bruson Oct. 17, 19392,213,477 Steindorf et a1. Sept; 3, 1940 2,425,755 Roberts et a1. Aug.19, 1947 2,425,845 Toussaint et a1. Aug. 19, 1947

1. AT LEAST ONE COGENERIC MIXTURE OF A HOMOLOGOUS SERIES OF GLYCOLETHERS OF APLAHA-TERPINEOL; SAID COGENERIC MIXTURE BEING DERIVEDEXCLUSIVELY FROM ALPHA-TERPINEOL, GLYCIDE, ETHYLENE OXIDE AND PROPLENEOXIDE BY REACTION THEREOF IN SUCH WEIGHT PROPORTIONS SO THE AVERAGECOMPOSITION OF SAID COGENERIC MIXTURE STATED IN TERMS OF INITIALREACTANTS LIES APPROXIMATELY WITHIN THE TRUNCATED TRAPEZOIDAL PYRAMIDIDENTIFIED AS E, F, G, HI, J, K, L IN FIGURE 4 OF THE DRAWINGS, WITH THEPROVISO THAT THE PERCENTAGE OF GLYCIDE IS WITHIN THE LIMITS OF 2% TO 25%BY WEIGHT AND THAT THE REMAINING THREE LIMITS REACTANTS, RECALCULATED TOA 100% BASIS, LIE APPROXIMATELY WITHIN THE TRAPEZOIDAL AREA DEFINEDAPPROXIMATELY IN FIGURE 3 OF THE DRAWINGS BY POINTS 8, 9, 10 AND 11.